Dispirotetradecanes

ABSTRACT

Dispirotetradecanes of the formula I ##STR1## wherein R 1  and R 2  are each independently of each other alkyl containing 1 to 12 carbon atoms wherein one or more non-adjacent CH 2  groups may also be replaced by --O--, --CO--, --CO--O--, --O--CO--, --O--COO-- and/or --CH═CH-- (trans), one of the radicals R 1  and R 2  also being H, F, Cl, Br, I, CN, NO 2 , NCS, 
     A 1  and A 2  are each independently of each other trans-1,4-cyclohexylene wherein one or two non-adjacent CH 2  groups may be replaced by --O-- and/or --S--, or 1,4-phenylene wherein one or more CH groups may also be replaced by N, with it also being possible optionally for A 1  and A 2  to be substituted laterally or axially by F, Cl, CN, CH 3 , 
     Z 1  and Z 2  are each independently of each other --C--O--, --O--CO--, --CH 2  CH 2  --, --CH 2  O--, --OCH 2  -- or a single bond, 
     m and n are each 0, 1 or 2, 
     (m+n) 0, 1 or 2, 
     X 1 , X 2 , X 3  and X 4  are each independently of each other H, F, Cl or CN, and one or both of the groups CX 1  X 2  and CX 3  X 4  may also be C═O, may be used as components of liquid-crystalline phases.

The invention relates to dispirotetradecanes of the formula I ##STR2##wherein

R¹ and R² are each independently of the other alkyl containing 1 to 12carbon atoms wherein one or more non-adjacent CH₂ groups may also bereplaced by --0--, --CO--, --CO--O--, --O--CO--, --O--COO-- and/or--CH═CH-- (trans), one of the radicals R¹ and R² also being H, F, Cl,Br, I, CN, NO₂, NCS,

A¹ and A² are each independently of the other trans1,4-cyclohexylenewherein one or two nonadjacent CH₂ groups may be replaced by --O--and/or --S--, or 1,4-phenylene wherein one or more CH groups may also bereplaced by N, with it also being possible optionally for A¹ and A² tobe substituted laterally or axially by F, Cl, CN, CH₃,

Z¹ and Z² are each independently of the other --CO--O--, --O--CO--,--CH₂ CH₂ --, --CH₂ O--, --OCH₂ -- or a single bond,

m and n are each 0, 1 or 2,

(m+n) 0, 1 or 2,

N¹, X², X³ and X⁴ are each independently of the other H, F, Cl or Cn,and one or both of the groups CX¹ X² and CX³ X⁴ may also be C═O, withthe proviso that (m+n) is 1 or 2 if both groups CX¹ X² and CX³ X⁴ areC═O.

For the sake of simplicity, in what follows Cy is a 1,4-cyclohexylenegroup, Dio is a 1,3-dioxane-2,5-diyl group, Dit is a1,3-dithiane-2,5-diyl group and Phe is a 1,4-phenylene group.

Similar compounds are known, for example, from GermanOffenlegungsschrift No. 3,426,035 and German Offenlegungsschrift No.3,407,013. However, in contrast to the present compounds, the compoundsspecified there always contain cyclohexane rings linked via a singlebond while the novel compounds always have the dispirotetradecanestructure.

The compounds of the formula I can be used like similar compounds ascomponents of liquid-crystalline phases, in particular for displayswhich are based on the principle of the twisted cell (TN displays), theguest-host effect, the aligned phase deformation effect, the dynamicscattering effect or the SSFLC principle.

The invention was based on the object of finding novel stableliquid-crysalline or mesogenic compounds which are suitable ascomponents of liquid-crystalline phases.

It has now been found that the compounds of the formula I are eminentlysuitable as components of liquid-crystalline phases. In particular, theyare suitable for wide-range mixtures with particularly low opticalanisotropy.

In addition, the provision of the compounds of the formula Isubstantially widens, quite generally, the range of liquid-crystallinesubstances which are suitable for producing liquid-crystalline mixturesfrom various application points of view.

The compounds of the formula I have a wide field of application.Depending on the choice of substituents, these compounds can act as basematerials of which liquid-crystalline phases are predominantly composed;however, compounds of the formula I may also be added toliquid-crystalline base materials from other compound categories inorder, for example, to optimize the dielectric and/or optical anisotropyor other parameters of such a dielectric. The compounds of formula I forfurthermore suitable as intermediate products for preparing othersubstances which can be used as constituents of liquid-crystallinephases. In the pure state, the compounds of the formula I are colorlessand form liquid-crystalline mesophases in a temperature range which isfavorably situated for electrooptical use. They are very stablechemically, thermally and towards light.

The subject of the invention is therefore formed by the compounds of theformula I and also by a method for producing them, wherein suitablysubstituted cyclohexanecarboxylic acid halides are converted into theketenes by dehydrohalogenation and the latter are dimerized to thedispirotetradecanedione system, or wherein one or both C═O groups in acompound which otherwise corresponds to the formula I but contains twoC═O groups in the 7,14 position are treated with a reducing agent, orwherein, to produce esters of the formula I (wherein R¹ and/or R² is analkyl group wherein one or more CH₂ groups are replaced by --O--CO--groups and/or --CO--O-- groups and/or wherein Z¹ and/or Z² is --CO--O--or --O--CO--), a corresponding carboxylic acid or one of its reactivederivatives is reacted with a corresponding alcohol or one of itsreactive derivatives, or wherein, to produce 1,3-dioxane derivatives or1,4-dithiane derivatives of the formula I (wherein A¹ and/or A² is1,3-dioxane-2,5-diyl or 1,3 -dithiane-2,5-diyl), a correspondingaldehyde is reacted with a corresponding diol or dithiol, or wherein toproduce ethers of the formula I (wherein R¹ and/or R² is an alkyl groupwherein one or more CH₂ groups are replaced by O atoms and/or Z¹ and/orZ² is an --OCH₂ -- or --CH₂ O-- group), a corresponding hydroxylcompound is esterified, or wherein, to produce nitrites of the formula I(wherein X¹, X², X³ and/or X⁴ is CN), the corresponding chlorine orbromine compounds are reacted with a cyanide.

Furthermore, the subject of the invention is the use of compounds of theformula I ##STR3## wherein

R¹ and R² are each independently of the other alkyl containing 1 to 12carbon atoms wherein one or more non-adjacent CH₂ groups may also bereplaced by --O--, --CO--, --CO--O--, --O--CO--, --O--COO-- and/or--CH═CH-- (trans), one of the radicals R¹ and R² also being H, F, Cl,Br, I, CN, NO₂, NCS,

A¹ and A² are each independently of the other trans1,4-cyclohexylenewherein one or two nonadjacent CH₂ groups may be replaced by --O--and/or --S--, or 1,4-phenylene wherein one or more CH groups may also bereplaced by N, with it also being possible optionally for A¹ and A² tobe substituted laterally or axially by F, Cl, CN, CH₃,

Z¹ and Z² are each independently of the other --CO--O--, --O--CO--,--CH₂ CH₂ --, --CH₂ O--, --OCH₂ -- or a single bond,

m and n are each 0, 1 or 2,

(m+n) 0, 1 or 2,

X¹, X², X³ and X⁴ are each independently of the other H, F, Cl or CN,and one or both of the groups CX¹ X² and CX³ X⁴ may also be C═O, ascomponents of liquid-crystalline phases with a particularly low opticalanisotropy, preferably with Δn≦0.09, in particular Δn≦0.08. The subjectof the invention is also formed by liquid-crystalline phases containingat least two liquid-crystalline components, wherein at least onecomponent of the phase is a compound containing the structural element##STR4## wherein X¹, X², X³ and X⁴ are each independently of the otherH, F, Cl or CN and one or both of the groups CX¹ X² and CX³ X⁴ may alsobe C═O. The subject of the invention is furthermore formed byliquid-crystalline phases with a content of at least one compound of theformula I and also liquid-crystalline display elements, in particularelectrooptical display elements which contain such phases.

Above and below, R¹, R², A¹, A², Z¹, Z², X¹, X², X³, X⁴, m and n havethe specified meaning unless anything else is expressly noted.

The compounds of the formula I include compounds of the partial formulaeIa to Id: ##STR5##

Of these, those of the partial formulae Ia and Id are particularlypreferred.

The structural element ##STR6## is preferably ##STR7##

Particularly preferred are the structural elements 1, 2, 3, 5, 7, 9, 10,12, 14 and 15, in particular 1, 2 and 3.

The preferred compounds of the partial formula Ia include those of thepartial formulae Iaa to Iag: ##STR8##

Of these, those of the partial formulae Iab, Iae and Iag areparticularly preferred.

The preferred compounds of the partial formula Ib include those of thepartial formulae Iba to Ibd: ##STR9##

In the partial formulae Iba to Ibd, Z¹ is primarily a single bond andsecondarily --CO--O-- or --O--CO--, X¹ -X⁴ are preferably H andfurthermore also Cl, F or CN, and one or both of the groups CX¹ X² andCX³ X⁴ may also be C═O.

Of these, those of the partial formula Iba are particularly preferred.

The preferred compounds of the partial formula Ic include those of thepartial formulae Ica to Icd: ##STR10##

In Ica to Icd, Z¹ is preferably a single bond but furthermore also--CO--O-- or --O--CO--, X¹ -X⁴ are preferably H, but furthermore alsoCl, F or CN, and one or both of the groups CX¹ X² and CX³ X⁴ may also beC═O.

Of these, those of the partial formulae Ica and Icd are particularlypreferred.

The preferred compounds of the partial formula Id include those of thepartial formulae Ida to Ide: ##STR11##

In the partial formulae Ida to Ide, Z¹ and/or Z² are primarily singlebonds and secondarily --CO--O-- or --O--CO--; X¹ -X⁴ are preferably H,but furthermore also Cl, CN or F; one or both of the groups CX¹ X² andCX³ X⁴ may also be C═O.

Of these, those of the partial formula Ida are particularly preferred.

In the compounds of the formulae above and below, R¹ and R² arepreferably alkyl, --O--alkyl, --OCO--alkyl or --COO--alkyl, inparticularly alkyl, and if linked to Phe, also CN, F, NCS, NO₂.

A¹ and A² are preferably Cy or Phe.

Z¹ and Z² are preferably single bonds, furthermore preferably also--CO--O--, --O--CO--, --CH₂ O--, --OCH₂ -- or --CH₂ CH₂ -- groups.

X¹ -X⁴ are preferably H, furthermore F, Cl or CN.

Furthermore, one or both of the groups CX¹ X² and CX³ X⁴ may also be aC═O group.

If CX¹ X² and CX³ X⁴ are C═O, (m+n) is 1 or 2.

m and n are preferably 0 or 1.

The alkyl radicals in the groups R¹ and/or R² may be straight-chain orbranched. Preferably, they are straight-chain, contain 1, 2, 3, 4, 5, 6,7, 8, 9 or 10 carbon atoms and therefore denote preferably methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl,furthermore undecyl or dodecyl.

If R¹ and/or R² are alkyl radicals in which preferably one ("alkoxy" or"oxaalkyl") or two ("alkoxy-alkoxy" or "dioxaalkyl") CH₂ groups arereplaced by O atoms, they may be straight-chain or branched. Preferably,they are straight-chain, contain 2, 3, 4, 5, 6 or 7 carbon atoms andtherefore are preferably ethoxy, propoxy, butoxy, pentoxy, hexoxy,heptoxy, 2-oxapropyl (═methoxymethyl), 2- (═ethoxymethyl) or 3-oxabutyl(═2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-,3-, 4-, 5- or 6-oxaheptyl, furthermore methoxy, octoxy, nonoxy, decoxy,2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl,2-, 3-, 4-, 5-, 6-, 7-, 8 - or 9-oxadecyl, 1,3-dioxabutyl(═methoxy-methoxy), 1,3-, 1,4- or 2,4-dioxapentyl, 1,3-, 1,4-, 1,5-,2,4- or 3,5-dioxahexyl, 1,3-, 1,4-, 1,5-, 1,6-, 2,4-, 2,5-, 2,6-, 3,5-,3,6- or 4,6-dioxaheptyl.

Compounds of the formula I and also of the partial formulae above andbelow with branched wing groups R¹ or R² may occasionally be ofimportant because of a better solubility in the usual liquid-crystallinebase materials, in particular, however, as chiral dopants if they areoptically active. Such compounds are furthermore suitable as componentsof ferroelectric liquid-crystalline phases. Branched groups of this typecontain as a rule not more than one chain branching. Preferred branchedradicals R¹ are isopropyl, 2-butyl (═1-methylpropyl), isobutyl(═2-methylpropyl), 2-methylbutyl, isopentyl (═3-methylbutyl),2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl,isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy,2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy,1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 2-octyloxy.

The compounds of the formula I are prepared by methods known per se suchas are described in the literature (for example, in the standard workssuch as Houben Weyl, Methoden der organischen Chemie (Methods of OrganicChemistry), Georg-Thieme-Verlag, Stuttgart) and in particular, underreaction conditions which are known and suitable for the reactionsmentioned. At the same time, use may also be made of variants which areknown per se but are not mentioned here.

Those skilled in the art may also draw on synthesis methods from theprior art through routine methods (for example, Japanese Pat. No.59-152343 relating to the dispiro(5.1.5.1)tetradecane-7,14-diones; theGerman Offenlegungsschriften Nos. 2,344,732, 24,540,088, 2,429,093,2,502,304, 2,636,684, 2,701,591 and 2,752,975 relating to compoundscontaining 1,4-cyclohexylene and 1,4-phenylene groups; GermanOffenlegungsschriften Nos. 2,944,905 and 3,227,916 relating to compoundscontaining 1,3-dioxane-2,5-diyl groups; and for example, GermanOffenlegungsschrift No. 3,201,721 relating to compounds containing --CH₂CH₂ -- bridging links).

The starting materials may, if desired, also be formed in situ in amanner such that they are not isolated from the reaction mixture but areimmediately converted into the compounds of the formula I.

Thus, the compounds of the formula I can be prepared bydehydrohalogenating substituted cyclohexanecarboxylic acid halides in aninert solvent such as, for example, benzene, toluene, by means of a basewhile heating, and dimerizing the ketene produced to formdispirotetradecanedione.

Furthermore, the compounds of the formula I may be prepared by treatingone or both keto groups in appropriate 3,11-disubstituteddispirotetradecane-7,14-diones, which can be prepared, for example, byketene dimerization, with a reducing agent. To introduce halogensubstituents, the dispirotetradecanedione is preferably reacted in aninert solvent such as, for example, carbon tetrachloride, chloroform,ether, with an inorganic acid halide, for example phosphoruspentachloride, phosphorus pentabromide, at temperatures of 0°-100°,preferably at room temperature.

Compounds of the formula I may also be prepared by reducing a compoundwhich otherwise corresponds to the formula I, but contains instead of Hatoms one or more reducible groups and/or C--C bonds.

As reducible groups, carbonyl groups are preferably suitable, inparticular keto groups, furthermore for example, free or esterifiedhydroxy groups or aromatically bonded halogen atoms. Preferable startingsubstances for the reduction correspond to the formula 1, but maycontain, instead of a cyclohexane ring, a cyclohexene ring orcyclohexanone ring and/or, instead of a --CH₂ CH₂ -- group, a --CH═CH--group and/or, instead of a --CH₂ -- group, a --CO-- group and/or,instead of an H atom, a free or a functionally modified OH group (forexample in the form of its p-toluenesulfonate). The carbonyl groups ofthe dispiro compound in the 7- and 14-position may also be reduced byusual reduction methods.

The reduction may, for example, take place by catalytic hydrogenation attemperatures between about 0° and about 200° and also pressures betweenabout 1 and 200 bar in an inert solvent, for example an alcohol such asmethanol, ethanol or isopropanol, an ether such as tetrahydrofuran (THF)or dioxane, an ester such as ethyl acetate, a carboxylic acid such asacetic acid or a hydrocarbon such as cyclohexane. Suitable as catalystsare expediently noble metals such as Pt or Pd which may be used in theform of oxides (for example PtO₂, PdO), on a carrier (for example Pd oncharcoal, calcium carbonate or strontium carbonate) or in a finelydivided form.

Ketones can also be reduced to the corresponding compounds of theformula I which contain alkyl groups and/or --CH₂ CH₂ bridges by themethods of Clemmensen (with zinc, amalgamated zinc or zinc andhydrochloric acid, expediently in aqueous-alcoholic solution or in aheterogeneous phase containing water/toluene at temperatures betweenabout 80° and 120° C.) or of Wolff-Kishner (with hydrazine, expedientlyin the presence of alkali such as KOH or NaOH in a high-boiling solventsuch as diethylene glycol or triethylene glycol at temperatures betweenabout 100° and 200° C.). With the sensitivity of the four-ring diketone,these methods may not be successful in certain cases (depending on thesubstitution). In such cases, more gentle methods must be used(reduction of the dihalides with sodium or of the thioketones orthioketals with Raney nickel).

Furthermore, reduction with complex hydrides is possible. For example,arylsulfonyloxy groups may be removed reductively with LiAlH₄, and inparticular ptoluenesulfonyloxymethyl groups can be reduced to methylgroups, expediently in an inert solvent such as diethyl ether or THF attemperatures between about 0° and 100° C. Double bonds may also behydrogenated (even in the presence of CN groups-) with NaBH₄ ortributyltin hydride in methanol.

Esters of the formula I (R¹ and/or R² =alkyl, wherein one or more CH₂groups are replaced by --O--CO-- and/or --CO--O-- groups and/or Z¹ andZ² =--CO--O-- or --O--CO--) can also be obtained by esterification ofcorresponding carboxylic acids (or their reactive derivatives) withalcohols or phenols (or their reactive derivatives).

Acid halides, in particular the chlorides and bromides, furthermore theanhydrides, azides or esters, in particular alkyl esters containing 1-4carbon atoms in the alkyl group are suitable as reactive derivatives ofthe carboxylic acids mentioned.

In particular, the corresponding metal alcoholates or phenolates,preferably of an alkali metal such as Na or K, are suitable as reactivederivatives of the alcohols or phenols mentioned.

the esterification is advantageously carried out in the presence of aninert solvent. In particular ethers such as diethyl ether, di-n-butylether, THF, dioxane or anisole, ketones such as acetone, butanone orcyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide,hydrocarbons such as benzene, toluene or xylene, halogenatedhydrocarbons such as carbon tetrachloride or tetrachloroethylene andsulfoxides such as dimethylsulfoxide or sulfolane are well suited.Solvents which are not miscible with water may at the same timeadvantageously be used for azeotropically distilling off the waterformed during the esterification. Occasionally, an excess of an organicbase, for example pyridine, quinoline or triethylamine, may also be usedas a solvent for the esterification. The esterification can also becarried out in the absence of a solvent, for example by simply heatingthe components in the presence of sodium acetate. The reactiontemperature is usually between -50° and +250° C., preferably between-20° and +80°. At these temperatures, the esterification reactions areas a rule complete after 15 minutes to 48 hours.

In detail, the reaction conditions for the esterification dependsubstantially on the nature of the starting substances used. Thus, afree carboxylic acid is reacted with a free alcohol or phenol as a rulein the presence of a strong acid, for example a mineral acid such ashydrochloric acid or sulfuric acid. A preferred mode of reaction is thereaction of an acid anhydride or, in particular, an acid chloride withan alcohol, preferably in a basic medium, in particular alkali metalhydroxides, such as sodium or potassium hydroxide, alkali metalcarbonates or hydrogencarbonates, such as sodium carbonate, sodiumhydrogencarbonate, potassium carbonate or potassium hydrogencarbonate,alkali metal acetates such as sodium or potassium acetate, alkalineearth metal hydroxides such as calcium hydroxide or organic bases suchas triethylamine, pyridine, lutidine, collidine or quinoline being ofimportance as bases. A further preferred embodiment of theesterification consists in converting the alcohol or the phenol firstinto the sodium or potassium alcoholate or phenolate, for example bytreatment with ethanolic sodium or potassium hydroxide, isolating thisand suspending it together with sodium hydrogencarbonate or potassiumcarbonate in acetone or diethyl ether with stirring, and mixing thissuspension with a solution of the acid chloride or anhydride in diethylether, acetone or DMF, expediently at temperatures between about -25°and +20°.

Dioxane derivatives or dithiane derivatives of the formula I (whereinone of the groups A¹ and/or A² is a 1,3-dioxane-2,5-diyl group or a1,3-dithiane-2,5-diyl group) are expediently prepared by reaction of acorresponding aldehyde with a corresponding 1,3-diol or a corresponding1,3-dithiol (or one of its reactive derivatives), preferably in thepresence of an inert solvent such as benzene or toluene and/or acatalyst, for example a strong acid such as sulfuric acid, benzene- orp-toluenesulfonic acid, at temperatures between about 20° and about150°, preferably between 80° and 120° C. Acetals are primarily suitableas reactive derivatives of the starting substances.

The aldehydes, 1,3-diols and 1,3-dithiols mentioned and also theirreactive derivatives are in some cases known, and in some cases they canbe prepared without difficulty by standard methods of organic chemistryfrom compounds known from the literature. For example, the aldehydes canbe obtained by oxidizing corresponding alcohols or by reducingcorresponding carboxylic acids or their derivatives, the diols byreducing corresponding diesters, and also the dithiols by reactingcorresponding dihalides with NaSH.

Ethers of the formula I (wherein R¹ and/or R¹ is an alkyl group, whereinone or more CH₂ groups are replaced by 0 atoms, and/or wherein Z¹ and/orZ² is an --OCH₂ -- or a --CH₂ O group) can be obtained by etherifyingcorresponding hydroxyl compounds, preferably corresponding phenols, thehydroxyl compound expediently being converted first into a correspondingmetal derivative, for example by treatment with NaH, NaNH₂, NaOH, KOH,Na₂ CO₃ or K₂ CO₃ to the corresponding alkali metal alcoholate or alkalimetal phenolate. This may then be reacted with the corresponding alkylhalide, sulfonate or dialkyl sulfonate, expediently in an inert solventsuch as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or alsoin an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperaturesbetween about 20° and 100°.

To prepare nitriles of the formula I (wherein X¹ and/or X² and/or X³and/or X⁴ is CN), corresponding chlorine or bromine compounds of theformula I may be reacted with a cyanide, expediently with a metalcyanide such as NaCN, KCN or Cu₂ (CN)₂, for example in the presence ofpyridine in an inert solvent such as DMF or N-methylpyrrolidone attemperatures between 20° and 200°.

The novel liquid-crystalline phases consist of 2 to 15, preferably 3 to15 components, including at least one compound of the formula I. Theother constituents are preferably selected from the nematic ornematogenic substances, in particular the known substances, from thecategories of the azoxybenzenes, benzylideneanilines, biphenyls,terphenyls, phenylbenzoates or cyclohexylbenzoates, phenyl or cyclohexylesters of cyclohexanecarboxylic acid, phenylcyclohexanes,cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes,1,4-biscyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl- orcyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, phenyl- orcyclohexyl-1,3-dithianes, 1-phenyl-2-cyclohexylethanes, optionallyhalogenated stilbenes, benzyl phenyl ether, tolanes and substitutedcinnamic acids.

The most important compounds suitable as constituents of suchliquid-crystalline phases may be characterized by the formula II,

    R'-L-G-E-R"                                                II

wherein L and E are each a carbo- or heterocyclic ring system from thegroup formed from 1,4-disubstituted benzene and cyclohexane rings,4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexanesystems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings,2,6-disubstituted napthalene, di- and tetrahydronaphthalene, quinazolineand tetrahydroquinazoline, G is

    ______________________________________                                        CHCH             N(O)N                                                        CHCY             CHN(O)                                                       CC               CH.sub.2 CH.sub.2                                            COO              CH.sub.2 O                                                   COS              CH.sub.2 S                                                   CHN              COOPheCOO                                                    ______________________________________                                    

or a single C--C bond, Y is halogen, preferably chlorine, or CN, and R'and R" are alkyl, alkoxy, alkanoyloxy or alkoxycarbonyloxy containing upto 18, preferably up to 8 carbon atoms, or one of these radicals is alsoCN, NC, NO₂, CH₃, F, Cl or Br.

In most of these compounds, R' and R" are different from each other, oneof these radicals mostly being an alkyl or alkoxy group. However, othervariants of the substituents envisaged are also common. Many suchsubstances or also mixtures thereof are obtainable commercially. Allthese substances can be prepared by methods known from the literature.

The novel phases contain about 0.1 to 99, preferably 10 to 95%, of oneor more of the compounds of the formula I.

Furthermore, novel dielectrics containing 0.1 to 40, preferably 0.5 to30%, of one or more compounds of the formula I are preferred.

The preparation of the novel dielectrics takes places in a manner whichis known per se. As a rule, the components are dissolved in each other,expediently at elevated temperature.

The liquid-crystalline dielectrics according to the invention may bemodified by suitable additives so that they can be used in all the typesof liquid-crystalline display elements which have become known hitherto.

Such additives are known to those skilled in the art and are describedcomprehensively in the literature. For example, supporting electrolytes,preferably ethyldimethyldodecylammonium 4-hexyloxybenzoate,tetrabutylammonium tetraphenylboranate or complex salts of crown ethers(cf., for example, I. Haller et al., Mol. Cryst. Liq. Cryst., vol. 24,pages 249-258 (1973)) may be added to improve the conductivity, dichroicdyestuffs to produce colored guest-host systems or substances to modofythe dielectric anisotropy, the viscosity and/or the orientation of thenematic phases. Such substances are, for example, described in theGerman Offenlegungsschriften Nos. 2,209,127, 2,240,854, 2,321,632,2,338,281, 2,450,088, 2,637,430, 2,853,728 and 2,902,177.

The examples which follow are intended to explain the invention withoutrestricting it. m.p.=melting point, c.p.=clearing point. Percentage dataabove and below are percentages by weight; all temperatures arespecified in degrees Celsius. K denotes crystalline state, N denotesnematic and I denotes isotropic state. The numbers between K, N and Irepresent the transition temperatures.

EXAMPLE 1

3.0 g of triethylamine in 100 ml of benzene are added dropwise withstirring to a mixture of 5.4 g oftrans-4-(trans-4-n-propylcyclohexyl)cyclohexanecarboxylic acid chlorideand 50 ml of benzene, and stirring is then carried out for 8-24 h underreflux. After separating off the triethylammonium chloride, the filtrateis washed until neutral and the organic phase worked up. Afterrecrystallization,3,11-bis(trans-4-n-propylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dioneis obtained and after chromatographic separation of the isomers, thepure trans-dispiro compound is obtained with m.p. of 290°.

The following are prepared analogously:

3,11-bis(trans-4-methylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-ethylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-butylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-pentylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-hexylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-heptylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-octylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-nonylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-decylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-methoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-ethoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-propoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-butoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-pentoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-hexoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-heptoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-octoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-nonoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(trans-4-decoxycyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-methylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-ethylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-propylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-butylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-pentylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-hexylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-heptylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-octylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-nonylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-decylphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-methoxyphenyl)dispiro[5.1.5.1]tetradecnae-7,14-dione

3,11-bis(4-ethoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-propoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-butoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-pentoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-hexoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-heptoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-octoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-nonoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3,11-bis(4-decoxyphenyl)dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-hexylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-ethylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-butylcyclohexyl)-11-(trans-4-nonylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-decylcyclohexyl)-11-(trans-4-hexylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-pentylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-dispiro[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-butylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-propylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-pentylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-ethylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-methylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-pentylcyclohexyl)-11-trans-methyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-(trans-4-heptylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-methylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transmethyldispiro[5.1.5.1]tetradecane-7,14-dione

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecane-7,14-dione.

EXAMPLE 2

1 mmol of3,11-bis(trans-4-propylcyclohexyl)dispiro-[5.1.5.1]tetradecane-7,14-dione(obtainable according to Example 1) are stirred with 210 mg (1 mmol) ofphosphorus pentachloride in 30 ml of carbon tetrachloride for 48 hoursat room temperature. After pouring onto ice-water, the organic phase isworked up. After chromatographic purification,3,11-bis(trans-4-propylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1.]tetradecan-7-oneis obtained, m.p. 159°, c.p. 266.7°-270.1°.

The following are prepared analogously:

3,11-bis(trans-4-methylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-ethylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-butylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-pentylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-hexylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-heptylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-octylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-nonylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-decylcyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-methoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-ethoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-propoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-butoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-pentoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-hexoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-heptoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-octoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-nonoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(trans-4-decoxycyclohexyl)-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3,11-bis(4-methylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-ethylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-propylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-butylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-pentylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-hexylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-heptylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-octylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-nonylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-decylphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-methoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-ethoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-propoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-butoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-pentoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-hexoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-heptoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-octoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-nonoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3,11-bis(4-decoxyphenyl)-14,14-dichlorodispiro[5.1.5.1]-tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-(trans-4-nonylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-decylcyclohexyl)-11-(trans-4-hexylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one.

EXAMPLE 3

Analogously to Example 2, the3,11-trans-dipentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one, m.p.290°, c.p. 21° is obtained from3,11-trans-dipentyldispiro[5.1.5.1]tetradecane-7,14-dione (obtainableaccording to Japanese Patent No. 59-152343).

The following are prepared analogously:

3,11-trans-dimethyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one, K67° I

3,11-trans-diethyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipropyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one, m.p.46°, c.p. -40° (extr.)

3,11-trans-dibutyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dihexyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diheptyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dioctyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dinonyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-didecyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dimethoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diethoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipropoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dibutoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipentoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dihexoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diheptoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dioctoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dinonoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3,11-trans-didecoxy-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-trans-methyl-11-trans-propyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3-trans-propyl-11-trans-pentyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3-trans-butyl-11-trans-ethyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-on

3-trans-pentyl-11-trans-heptyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3-trans-octyl-11-trans-propyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

3-trans-propyl-11-trans-ethyl-14,14-dichlorodispiro-[5.1.5.1]tetradecan-7-one

EXAMPLE 4

A mixture of 1 mmol of3,11-bis(trans-4-propylcyclohexyl)dispiro[5.1.5.1]tetradecane-7,14-dithione(preparable by reaction of the corresponding diketone with P₄ S₁₀) and25 ml of tetrahydrofuran is added at room temperature to a well stirredsuspension of fresh Raney nickel in THF and stirred for 24 h at roomtemperature. The usual working up yields3,11-bis(trans-4-propylcyclohexyl)dispiro[5.1.5.1]tetradecane.

The following are prepared analogously:

3,11-bis(trans-4-methylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-ethylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-butylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-pentylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-hexylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-heptylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-octylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-nonylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-decylcyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-methoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-ethoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-propoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-butoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-pentoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-hexoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-heptoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-octoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-nonoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3,11-bis(trans-4-decoxycyclohexyl)dispiro[5.1.5.1]tetradecane

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-pentylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-dispiro[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecane

EXAMPLE 5

A mixture of 1.96 g of3,11-trans-dipentyldispiro-[5.1.5.1]tetradecane-7,14-dithione(obtainable by reaction of the corresponding diketone with P₄ S₁₀) and25 ml of THF are (sic) added at room temperature to a well stirredsuspension of fresh Raney nickel in THF and stirred for 24 h at roomtemperature. After the usual working up and recrystallization fromethanol, 3,11-trans-dipentyldispiro[5.1.5.1]tetradecane is obtained withm.p. 51° and c.p. 102°.

The following are prepared analogously:

3,11-trans-dimethyldispiro[5.1.5.1]tetradecane

3,11-trans-diethyldispiro[5.1.5.1]tetradecane

3,11-trans-dipropyldispiro[5.1.5.1]tetradecane

3,11-trans-dibutyldispiro[5.1.5.1]tetradecane

3,11-trans-dihexyldispiro[5.1.5.1]tetradecane

3,11-trans-diheptyldispiro[5.1.5.1]tetradecane

3,11-trans-dioctyldispiro[5.1.5.1]tetradecane

3,11-trans-dinonyldispiro[5.1.5.1]tetradecane

3,11-trans-didecyldispiro[5.1.5.1]tetradecane

3,11-trans-dimethoxydispiro[5.1.5.1]tetradecane

3,11-trans-diethoxydispiro[5.1.5.1]tetradecane

3,11-trans-dipropoxydispiro[5.1.5.1]tetradecane

3,11-trans-dibutoxydispiro[5.1.5.1]tetradecane

3,11-trans-dipentoxydispiro[5.1.5.1]tetradecane

3,11-trans-dihexoxydispiro[5.1.5.1]tetradecane

3,11-trans-diheptoxydispiro[5.1.5.1]tetradecane

3,11-trans-dioctoxydispiro[5.1.5.1]tetradecane

3,11-trans-dinonoxydispiro[5.1.5.1]tetradecane

3,11-trans-didecoxydispiro[5.1.5.1]tetradecane

3-trans-methyl-11-trans-propyldispiro[5.1.5.1]tetradecane

3-trans-propyl-11-trans-pentyldispiro[5.1.5.1]tetradecane

3-trans-butyl-11-trans-ethyldispiro[5.1.5.1]tetradecane

3-trans-pentyl-11-trans-heptyldispiro[5.1.5.1]tetradecane

3-trans-octyl-11-trans-propyldispiro[5.1.5.1]tetradecane

3-trans-propyl-11-trans-ethyldispiro[5.1.5.1]tetradecane

EXAMPLE 6

1 mmol of3-(trans-4-propylcyclohexyl)-11-transpentyldispiro[5.1.5.1]tetradecane-7,14-dione(obtainable according to Example 1 fromtrans-4-(p-propylcyclohexyl)-cyclohexanecarboxylic acid chloride andtrans-4-pentylcyclohexanecarboxylic acid chloride) is stirred with 210mg of phosphorus pentachloride in 30 ml of carbon tetrachloride for 48hours at room temperature. After pouring onto ice-water, the organicphase is worked up. After chromatographic purification,3-(trans-4-propylcyclohexyl)-11-trans-pentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan7-oneis obtained.

The following are prepared analogously:

3-(trans-4-propylcyclohexyl)-11-trans-propyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-ethyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-butyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-butyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-hexyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-pentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-pentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-propyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-methyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-heptyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one.

EXAMPLE 7

According to Example 6, starting from3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-pentyldispiro[5.1.5.1]tetradecane-7,14-dione(preparable according to Example 1 fromtrans-4-pentylcyclohexanecarboxylic acid chloride andtrans-4-(p-propylcyclohexyl)cyclohexylcyclohexanecarboxylic acidchloride),3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-pentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-oneis obtained.

The following are prepared analogously:

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-propyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-ethyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-butyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-pentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-propyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-trans-butyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-methylcyclohexyl)cyclohexyl]-11-trans-propyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-methyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-trans-heptyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one.

EXAMPLE 8

Analogously to Example 4,3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-pentyldispiro[5.1.5.1]-tetradecaneis obtained starting from3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-pentyldispiro[5.1.5.1]-tetradecane-7,14-dithione.

The following are prepared analogously:

3-(trans-4-propylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecane

3-(trans-4-butylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecane

3-(trans-4-pentylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecane

3-(trans-4-ethylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecane

3-(trans-4-methylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecane

3-(trans-4-pentylcyclohexyl)-11-trans-methyldispiro-[5.1.5.1]tetradecane

3-(trans-4-heptylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecane.

EXAMPLE 9

Analogously to Example 4,3-[trans-4-(p-propylcyclohexyl)cyclohexyl-11-trans-pentyl-dispiro[5.1.5.1]-tetradecaneis obtained starting from3-[trans-4-(p-propylcyclohexyl)-11-trans-pentyldispiro[5.1.5.1]tetradecane-7,14-dithione.

The following are prepared analogously:

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-propyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-ethyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-butyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-trans-butyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-hexyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-pentyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-trans-pentyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-methylcyclohexyl)cyclohexyl]-11-trans-propyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-methyldispiro[5.1.5.1]tetradecane

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-trans-heptyldispiro[5.1.5.1]tetradecane.

EXAMPLE 10

With atmospheric moisture being excluded, a solution of 10 g of3,11-trans-dipentyldispiro[5.1.5.1]tetradecan-7-ol-14-one (preparablefrom 3,11-trans-dipentyl-[5.1.5.1]tetradecane-7,14-dione by reactionwith lithium aluminum hydride) in 50 ml of dichloromethane is added at10° C. to a solution of 5.2 g of diethylamino sulfur trifluoride in 30ml of dichloromethane. The reaction mixture is heated to roomtemperature in the course of 1 hour and allowed to stand for a furtherhour. It is then poured onto ice and extracted with dichloromethane.After washing the organic phases, evaporating off the solvent andrecrystallizing the residue,3,11-trans-dipentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one isobtained with m.p. 53° and c.p. 116°.

The following are prepared analogously:

3,11-trans-dimethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-diethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dipropyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dibutyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dihexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-diheptyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dioctyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dinonyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-didecyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dimethoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-diethoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dipropoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dibutoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dipentoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dihexoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-diheptoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dioctoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-dinonoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-trans-didecoxy-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-methyl-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-propyl-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-butyl-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-pentyl-11-trans-heptyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-octyl-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-trans-propyl-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-propylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-methylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-ethylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-butylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-pentylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-hexylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-heptylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-octylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-nonylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-decylcyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-methoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-ethoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-propoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-butoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-pentoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-hexoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-heptoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-octoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-nonoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(trans-4-decoxycyclohexyl)-7-fluorodispiro-[5.1.5.1]tetradecan-14-one

3,11-bis(4-methylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-ethylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-propylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-butylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-pentylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-hexylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-heptylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-octylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-nonylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-decylphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-methoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-ethoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-propoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-butoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-pentoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-hexoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-heptoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-octoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-nonoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3,11-bis(4-decoxyphenyl)-7-fluorodispiro[5.1.5.1]-tetradecan-14-one

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-ethylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-(trans-4-nonylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-decylcyclohexyl)-11-(trans-4-hexylcyclohexyl)-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-propylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-butylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-pentylcyclohexyl)-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-pentylcyclohexyl)-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-pentylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-pentylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-pentylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-hexylcyclohexyl)-11-trans-heptyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-ethylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-ethylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-ethylcyclohexyl)-11-trans-heptyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-heptylcyclohexyl)-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-heptylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-heptylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-methylcyclohexyl)-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-methylcyclohexyl)-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-(trans-4-methylcyclohexyl)-11-trans-hexyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-pentyl-7-fluoro-dispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-ethyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-pentyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-trans-butyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-methylcyclohexyl)cyclohexyl]-11-trans-propyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-trans-methyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-trans-heptyl-7-fluorodispiro[5.1.5.1]tetradecan-14-one

EXAMPLE 11

A mixture of 1.8 g of3,11-dipentyl-7-oxodispiro-[5.1.5.1]tetradecane-14-dithione (obtainablefrom the corresponding diketone by reactiong with P₄ S₁₀ in pyridine)and 25 ml of THF is added at room temperature to a well stirredsuspension of fresh Raney nickel in THF. The mixture is stirred for 5hours and worked up as usual. After recrystallization from ethanol,3,11-transdipentyldispiro[5.1.5.1]tetradecan-7-one is obtained with m.p.66° and c.p. 111°.

The following are prepared analogously:

3,11-trans-dimethyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diethyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipropyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dibutyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dihexyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diheptyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dioctyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dinonyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-didecyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dimethoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diethoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipropoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dibutoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dipentoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dihexoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-diheptoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dioctoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-dinonoxy-dispiro[5.1.5.1]tetradecan-7-one

3,11-trans-didecoxy-dispiro[5.1.5.1]tetradecan-7-one

3-trans-methyl-11-trans-propyl-dispiro[5.1.5.1]tetradecan-7-one

3-trans-propyl-11-trans-pentyl-dispiro[5.1.5.1]tetradecan-7-one

3-trans-butyl-11-trans-heptyl-dispiro[5.1.5.1]tetradecan-7-one

3-trans-pentyl-11-trans-heptyl-dispiro[5.1.5.1]tetradecan-7-one

3-trans-octyl-11-trans-propyl-dispiro[5.1.5.1]tetradecan-7-one

3-trans-propyl-11-trans-ethyl-dispiro[5.1.5.1]tetradecan-7-one

3,11-bis-(trans-4-methylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-propylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one, K338° I

3,11-bis-(trans-4-butylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-hexylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-heptylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-octylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-nonylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-decylcyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-methoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-ethoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-propoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-butoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-pentoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-hexoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-heptoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-octoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-nonoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3,11-bis-(trans-4-decoxycyclohexyl)-dispiro[5.1.5.1]-tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-dispiro[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-propylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-butylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-pentylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-ethylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-methylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-hexylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-propyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-ethyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-butyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-pentyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-hexyldispiro-[5.1.5.1]tetradecan-7-one

3-(trans-4-heptylcyclohexyl)-11-trans-heptyldispiro-[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-propylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-ethylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-butylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-pentylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-hexylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transpentyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transethyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transpropyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transbutyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transhexyldispiro[5.1.5.1]tetradecan-7-one

3-[trans-4-(p-heptylcyclohexyl)cyclohexyl]-11-transheptyldispiro[5.1.5.1]tetradecan-7-one

EXAMPLE 12

Analogously to Example 2, starting frrom3,11-bis-(trans-4-propylcyclohexyl)dispiro[5.1.5.1]tetradecan-7-one, thecorresponding3,11-bis(trans-4-propylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecaneis obtained with K 172° N 266° I.

The following are prepared analogously:

3,11-bis(trans-4-methylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-ethylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-butylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-pentylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-hexylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-heptylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-octylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-nonylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-decylcyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-methoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-ethoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-propoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-butoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-pentoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-hexoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-heptoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-octoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-nonoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(trans-4-decoxycyclohexyl)-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3,11-bis(4-propylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-methylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-ethylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-butylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-pentylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-hexylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-heptylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-octylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-nonylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-decylphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-methoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-ethoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-propoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-butoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-pentoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-hexoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-heptoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-octoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-nonoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-bis(4-decoxyphenyl)-7,7-dichlorodispiro[5.1.5.1]-tetradecane

3,11-trans-dipropyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dimethyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-diethyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dibutyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dipentyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dihexyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-diheptyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dioctyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dinonyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-didecyl-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dimethoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-diethoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dipropoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dibutoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dipentoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dihexoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-diheptoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dioctoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-dinonoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3,11-trans-didecoxy-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-methylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-ethylcyclohexyl)-11-(trans-4-pentylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-propylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-butylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-hexylcyclohexyl)-11-(trans-4-ethylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-ethylcyclohexyl)-11-(trans-4-heptylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-octylcyclohexyl)-11-(trans-4-propylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-butylcyclohexyl)-11-(trans-4-nonylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-(trans-4-decylcyclohexyl)-11-(trans-4-hexylcyclohexyl)-7,7-dichlorodispiro[5.1.5.1]tetradecane

3-trans-methyl-11-trans-propyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3-trans-propyl-11-trans-pentyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3-trans-butyl-11-trans-ethyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3-trans-pentyl-11-trans-hexyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3-trans-octyl-11-trans-pentyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

3-trans-propyl-11-trans-ethyl-7,7-dichlorodispiro-[5.1.5.1]tetradecane

The examples which follow relate to liquid-crystal-line phases.

Example A:

A liquid-crystalline phase consisting of:

17% p-trans-4-propylcyclohexylbenzonitrile,

16% trans-1-p-ethoxyphenyl-4-propylcyclohexane,

23% p-trans-4-pentylcyclohexylbenzonitrile,

12% trans-1-p-butoxyphenyl-4-propylcyclohexane,

17% 4-ethyl-4'-(trans-4-pentylcyclohexyl)biphenyl and

15%3,11-bis(trans-4-propylcyclohexyl)-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-onehas a c.p. of 85°.

Example B:

A liquid-crystalline phase consisting of

15% p-trans-4-propylcyclohexylbenzonitrile,

11% p-trans-4-butylcyclohexylbenzonitrile,

21% p-trans-4-pentylcyclohexylbenzonitrile,

15% 3,11-trans-dipentyl-14,14-dichlorodispiro[5.1.5.1]tetradecan-7-one,

21% 4-ethyl-4'-(trans-4-pentylcyclohexyl)biphenyl,

12% 4-(trans-4-pentylcyclohexyl-4'-(trans-4-propylcyclohexyl)-biphenyland

5% 4-cyano-4'-trans-4-pentylcyclohexyl)biphenyl has a c.p. of 98°.

We claim:
 1. A dispirotetradecane of the formula I ##STR12## wherein R¹and R² are each independently alkyl containing 1 to 12 carbon atomswherein one or more non-adjacent CH₂ groups may also be replaced by--O--, --CO--, --CO--O--, --O--CO--, --O-- COO-- and/or --CH═CH--(trans), and one of the radicals R¹ and R² can also be H, F, Cl, Br, I,CN, NO₂, or NCS,A¹ and A² are each independently trans-1,4-cyclohexylenewherein one or two nonadjacent CH₂ groups may be replaced by --O--and/or --S--, or 1,4-phenylene wherein one or more CH groups may also bereplaced by N, with it also being possible optionally for A¹ and A² tobe substituted laterally or axially by F, Cl, CN, or CH₃, Z¹ and Z² areeach independently --CO--O--, --O--CO--, --CH₂ CH₂ --, --CH₂ O--, --OCH₂-- or a single bond, m and n are each 0, 1 or 2, (m+n) 0, 1 or 2, X¹,X², X³ and X⁴ are each independently H, F, Cl or CN, and one or both ofthe groups CX¹ X² and CX³ X⁴ may also be C═O, with the proviso that(m+n) is 1 or 2 if both groups CX¹ X² and CX³ X⁴ are C═O.
 2. A compoundof claim 1, wherein X¹ -X⁴ are all H.
 3. A compound of claim 1, wherein(m+n) is O.
 4. A compound of claim 1, wherein R¹ and R² are eachindependently alkyl or alkoxy.
 5. A compound of claim 1, wherein X¹ andX² are each H and at least one of X³ and X⁴ is not H.
 6. A compound ofclaim 1, wherein X¹ and X² are C═O.
 7. In a liquid crystalline phasecomprising at least two liquid crystal components, the improvementwherein at least one component is a dispirotetradecane of claim
 1. 8. Aliquid-crystalline phase of claim 7 having an optical anisotropy Δn lessthan or equal to 0.09.
 9. In a liquid-crystalline display elementcomprising a liquid crystal phase, the improvement wherein the phase isone of claim
 7. 10. In a liquid-crystalline display element comprising aliquid crystal phase, the improvement wherein the phase is one of claim8.
 11. In an electrooptical display element comprising a liquid crystalphase, the improvement wherein the phase is one of claim
 7. 12. In anelectrooptical display element comprising a liquid crystal phase, theimprovement wherein the phase is one of claim 8.